Disazo dyes



Patented Feb. 7, 1933 UNITED A E N oF-Fla Ef WERNER LANGE, onDESSAU-ZIEBIGK IN ANHALT, GER-MANY, nssieuoitlro GEnERAL ANILINE WORKS,1170,01" NEW YORK, n. 2., A CORPORATION O DELAW RE- I msazo IIDYES NoDrawing. Application filed mini 14, 1931, Serial No. 530,139,and inGermany May?)19 1311".

My present invention relates to a process of manufacturing new disazodyes and to the dyes obtainable by this process.v More particularly itrelates to yellow dyes having a remarkable aflinity for cotton.

I have found that valuable yellow substantive cotton dyes are obtainableby hisdiazotizing one molecular proportion of diaminobenzoylamino) -ordi- (aminobenzoyl aminobenzoylamino) -compounds and by coupling thebis-diazo compound obtained with two'molecular proportions of a, singleor of differentyellow azo components,from which at least one bears inltsmolecule one or;several sulfonic or c'arboxylic acid groups.

These dyes correspond to the general formula of the benzene series.Correspondent compounds of the naphthalene series maybe -de,-

rived from 1.4-, 1.3-, 1.5-, and 2.7-diamino naphthalenes and sulfonicacids thereof. These aminobenzoyl or aminobenzoylamino-' benzoylcompounds are obtainable according to the well-known processes byreacting 1.3- or LL-nitrobenzoylchloride upon the 7 said diaminesi, byreducing the nitro group, and rcpeating'these reactions in the case'ofaminobenzoylaminobenzoyl derivatives.

As azo componentsselected in order to prov duce yellow; dyes, thefollowing maybe menphenyl) 3 methyl 5 -pyrazolone-,phenylmethylpyrazolonecarboxylic acids such as, for instance,l-phenyl-5-pyrazolone3-car ated or aminobenzoylaminobenzoylated'derivatives-ofrwhi h'serve to prepare the hisdiazo compound, I enumeratethe follow ing z-l/land l.3-diaminobenzene, l-Iiiethyl-2.6-diaminobenzene and the sulfonic acids of these diamines,diaminostilbenes, such as, for instance,4.4-'diaininostilbene-2;2'-disulfonic acid, diaminodiphenyl"ureas, suchas,

- for instance, 4.4-diaminodiphenylurea-3.3-

'disulfonic acid, benzidines such as, for in stance, 4.4-diaminobenzidine-2.2- or 3.3-disulfonic acid. All these compounds are in tendedto be included into the term diamine My invention is illustrated by theexamples following hereafter, thef parts weight: 7

. EmampZe'--1.44 .8

being by parts of sodium lu l-di- (4-aminobenzoylamino)'- benzene-2sulfonate V are. diazotized inc-the usual manner in thepresenceof'hydrochloric acid by addition'of 13.8 parts. of sodiumnitrite. he bis-diazo -V compound is run into a solution of 50.8 partsof 1- dsulfophenyl -3-methyl-5-pyrazolone kept alkaline by the presenceof'so'diuin carbonate The reaction mixture is stirred until the diazocompound is consumedythen the dye formed is separated by addition ofcommon salt.

Probably it corresponds to the formula:

' SOaH TF N It dyes cotton vivid green-yellow tints of excellentfastness to light and acids.

E wample 2?.By substituting for sodium '1.et-di (4 aminobenzoylamino)benzene-2- sulfonate the corresponding quantity of sodium 4.4'-(e-aminobenzoylamino) -diphenylurea- 3.8-disulfonate and by carrying outthe further performance of the reaction in strict accordance with thedetails given in Example and bis-diazotized by addition of hydrochlo ricacid and 13.8 parts of sodium nitrite.

The diazo compound is run ina cold solution of 50.8 parts of 1-(V-sulfophenyl) -3- nethylv 5-pyrazolone, alkaline by the presence ofsodium carbonate. The mixture is stirred until the diazo compoundisconsumed. The dye is separated in the usual manner. It corresponds tothe formula:

of 1- (4-sulfophenyl) -3-methyl-5-pyrazolone is added and the mixtureisstirred for about 1 hour until free pryazolone is no more detectable inthe solution. Then a solution of 17.7 parts'of aceto acetic anilidedissolved'in i parts of sodium hydroxide and water is added and stirringis continued for a further hour until this component, likewise, iscompletely consumed. Then the reaction mixture is warmed. and the dyeisseparated diazo compounds. In the case of dyes conby addition of salt.

Probably it corresponds to the formula:

O aH 7 It likewise dyes cotton vivid green-yellow tints fastto theaction of light.

E acample 5.89 parts of sodium di-( lamino benzol 4 aminobenzoylamin)stilbene-2.2-disulfonate (as obtainable, for instance, by the processdisclosed in German Patent No. 252,376) are dissolved in water SOgH anddye scotton yellow tints fast to the action of light.

It is obvious that my invention is not limited to the foregoing examplesor to the specific details given therein. In a manner completelyanalogous to that given in detail in the examples, I may, use one of theother aminobenzolated or aminobenzoylaminoben zoylated diaminesmentioned above in preparing a bis-diazo compound and in a completelyanalogous manner I may couple the latter with one or two of the yellowazo components enumerated above. In the case of manufacturing dis azodyes containing in their molecule two diiferent azo components,preferably in the first stage that component is reacted upon thedis-diazo compounds which couples more difficulty, such as, forinstance, aceto-acetic anisidide sulfonic acid, methylketol sulfonicacid or salicylic acid. Then a pyrazolone compound may be coupled'inthe-second stage,

since these compounds react more freely with tainingdifferent-end-cornponents, preferably one of the latter is a pyrazolonederivative,

since otherwise the shades obtained are too What I claim is 1. As newproducts the disazo'dyes corre-- sponding to the general formula:'

and COOH, and n stands for 0 or 1, said dyes dyeing cotton fastness tolight.

wherein A means an aromatic radicle of the benzene or naphthaleneseries,X and X stand 4:. As new productsthe disazo dyescorresponding to thegeneral formula:

wherein A means the radicle of a benzene sulfonic' acid, a diphenylureasulfonic acid, a

stilbene sulfonic acid or a diphenyl sulfonic acid, X means a pyrazoloneradicle and X the radicle of an azo component producing yellow shades ofthe group consisting of pyrazolones, aceto-a'cetic anilides,methylketol, salicylic acid, at least one of these end componentsbearing an acid radicle of the group consisting ofl-SO H and -COOH,' I

wherein A meansan aromatic radiole of the benzene or naphthalene series,X means a pyrazolone radicle and X the radicle of an azocomponent'producing yellow shades of the group consisting ofpyrazolones, acetoacetic anilides, methylketol, salicylic acid, at

least one of these end components bearing an acid radicle of the groupconsisting of SO H and COOH, and n stands for 0 or 1, said dyes dyeingcotton yellow tints of excellent fastness to light. 3. As new productsthe disazo dyes corresponding to the general formula:

and'n stands'for 0 or 1, said dyes dyeing cotton yellow tints ofexcellent fastness to light.

'5. As new productsthe dyes corresponding to the general formula: I

wherein A means an aromatic radicle of the benzene or naphthaleneseries, X and X. stand for the radicle of an azo component producinyellow shades of the group consisting o pyrazolones, aceto-aceticanilides, 'methylketol, salicylic acid, at least one of these endcomponents bearing an acid ,radicle of the group consisting of *SOgH andCOOH, andnstands for Q or 1, said dyes wherein A means the radicle of abenzene sulfonic acid, a diphenylurea sulfonic acid, a stilbene sulfonicacid or a diphenyl sulfonic acid, X and X stand for the radicle of anazo component producing yellow shades of the group consisting ofpyrazolones, aceto-acetic anilides, methylketol, salicylic acid, atleast one of these end components bearing an acid radicle of the groupconsisting of' -'-SO 'H dyeing cotton yellow tints of excellent fastnessto light.

6. As new products the-dyes corresponding .to the general formulawhere'A meansthe radicle of a benzene sulfonlc ac1d,-a dlphenylureasulfonic acid, a

stilbene sulfonic acid, or adiphenyl sulfonic acid, X and X stand forthe radicle of an azo component producing yellow'shadesof yellow tintsof excellent the group consisting of pyraz'olones, acetoacetic anilides,methylketol, salicylic acid, at

least one of these end components bearing an acid radicle of the groupconsisting SO3H and COOH, and t stands for 0 or 1, said dyes dyeingcotton yellow tints of excellent fastness to light.

7. As new products the dyes corresponding to the general formula:

wherein A means the radicle of a benzene sulfonic acid, a diphenyl ureasulfonic acid, a stilbene sulfonic acid, or a diphenyl sulfonic acid, Xstands for a pyrazolone radicle, X stands for the radicle of an azocomponent producing yellow shades of the group consisting ofpyrazolones, aceto-acetic anilides, methylketol, salicylic acid, atleast one of these end components bearing an acid radicle of the groupconsisting of -SO H and COOH, and n stands for 0 or 1, said dyes tonyellow tints of excellent fastness to light. 9. As a new product the dyecorresponding asfree acid to the formula:

dyeing cotton yellowtints of good fastness to light., r

10. As new p oducts the dyes correspond.-

ing to thegeneral formula: I

wherein A standsfor the radicle of-a benzene sulfonlc acld, adiphenylurea sulfonic acld,

a stilbene sulfonic acid or a diphenyl sulfonic dyeing cotton yellowtints of excellent fastness to light. I

8. As new products the dyes corresponding as free acid to the generalformula:

wherein A stands forthe radicle of a benzene sulfonic acid, adiphenylureasulfonic acid, a stilbene sulfonic acid or a diphenylsulfonic acid, X stands for a pyrazolone radicle and wherein A standsforthe radicle of a benzene sulfonic acid, a diphenylurea,sulfonic acid,a stilbene sulfonic acid or a diphenyl sulfonic acid, X stands fortheradicle of an azo component producing yellow shades of thegroupconsisting of cpyrazolones, aceto acetic anilides, methylketol,salicylic acid, and n stands for Ger 1, said dyes dyeing cot- X standsfor theradicle of an azo component producing, yellow shades of the groupconsisting of pyrazolones, aceto-acetic anilides, methylketol, salicylicacid; at least one of these end components bearing an acid radicle ofthe group consisting: of -SO H and -COOH, said dyesdyeing cotton yellowtints of excellent fastness to light. I a

12. As new products the dyes corresponding as free acid to the generalformula;

alkaline solution.

i co

5 i H H v H I X-N=NC O-k-A-l-O O-ON=N(IJOHI o=o \N/ wherein A stands forthe radicleofa ben- 16. The process which comprises bis-dizene sulfonicacid, a diphenylurea sulfonlc azotizing one molecular proportion of1.4-diacid, a stilbene sulfonic acid or a diphenyl (laminobenzoylamino)-benzene-2-sulfonic sulfonic acid and X stands for the radicle acid andcoupling the bis-diazo compound" of an azo component producing yellowshades with two molecular proportions of 1- sulof the group consistingof pyrazolones, aceto fophenyl) .-3-1nethyl-5-pyrazolone in a sodaaceticanilides, methylketol salicylic acid, alkaline solution. 7 said dyesdyeing cotton yellow tints or" excel- 17. 1 The process which comprisesbis-diazolent fastness to light. p r tizing one molecular proportion of4c. l-'di'- 13. As a new product the dye which vcorre-(-aminobenzoylamino) -diphenylurea-3 .3- sponds as free acid to theformula: disulfonic acid and coupling the bis-diazo H v l i H V Haawamgoaeg magenta-OH. II I 5 t} N o=o o= \N/ V 80:11 \N/.

said dye dyeing cotton vivid greenish-yellow compound with two molecularproportions of tints of excellent fastness to light and to acids. 1- (lsulfophenyl) -3-methyl-5-pyrazolone in p 1 1. As a new product the dyewhich correa soda-alkaline solution. I c sponds as free acid to theformula: 18. The process which compriseshis-diazop I I E i p =N ooNNH-OO-HN -0o i 2;; 1 0

\N/ SOaH sm so,H soln said dye dyeing cotton vivid greenish-yellowtizing one molecular proportion of di- (4- tints of excellent fastnessto light and to acids. amino-benzoyl-4-aminobenzoyl amino) -stil- 15.The process which comprises bis-diazobene disulfonic acid and couplingthe bis-ditizing one molecular proportion of an aroazo compound with twomolecular propormatic diamine of the general formula: tions of 1-(4-sulfophenyl) -3-methyl-5-py- H H l H V H I H(1 I-oqHr-oo),.1lI-c@moo-1lI-A-N--oo-ooH4 1 I -(oo-o@H4-1t .H,

wherein A means a radicle of the benzene or razolone in a soda-alkalinesolution. naphthalene series and 01 means 0 or 1 and 0011- In testimonywhereof, I afiix my signature. pling the bis-diazo compound with1.4'-sul- WERNER LANGE.

